Premium
Mechanistic Studies on the Salicylate‐Catalyzed Peroxyoxalate Chemiluminescence in Aqueous Medium
Author(s) -
Cabello Maidileyvis C.,
Souza Glalci A.,
Bello Liena V.,
Baader Wilhelm J.
Publication year - 2019
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/php.13180
Subject(s) - peroxyoxalate , chemiluminescence , chemistry , oxalate , photochemistry , anhydrous , hydrogen peroxide , catalysis , singlet state , aqueous solution , quantum yield , inorganic chemistry , fluorescence , organic chemistry , physics , quantum mechanics , nuclear physics , excited state
The peroxyoxalate reaction is one of the most efficient chemiluminescence transformations known and the only system occurring by an intermolecular chemically initiated electron exchange luminescence (CIEEL) mechanism with confirmed high quantum yields. The peroxyoxalate chemiluminescence (PO‐CL) is mainly studied in anhydrous organic medium; however, for bioanalytical application, it should be performed in aqueous media. In the present work, we study the peroxyoxalate system in a binary 1,2‐dimethoxyethane/water mixture with bis(2,4,6‐trichlorophenyl) oxalate (TCPO), bis(4‐methylphenyl) oxalate (BMePO) and bis[2‐(methoxycarbonyl)phenyl] oxalate (DMO), catalyzed by sodium salicylate, in the presence of rhodamine 6G as activator. Reproducible kinetic results are obtained for all systems; emission decay rate constants depend on the salicylate as well as hydrogen peroxide concentration, and the occurrence of a specific base catalysis is verified. Although singlet quantum yields determined are lower than in anhydrous media in comparable conditions, they are still considerably high and adequate for analytical applications. The highest singlet quantum yields are obtained for the “ecologically friendly” derivative DMO indicating that this derivative might be the most adequate substrate for the use of the peroxyoxalate system in bioanalytical applications.